CA2467422A1 - Perfluoropolyether additives - Google Patents
Perfluoropolyether additives Download PDFInfo
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- CA2467422A1 CA2467422A1 CA002467422A CA2467422A CA2467422A1 CA 2467422 A1 CA2467422 A1 CA 2467422A1 CA 002467422 A CA002467422 A CA 002467422A CA 2467422 A CA2467422 A CA 2467422A CA 2467422 A1 CA2467422 A1 CA 2467422A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
- C10M147/04—Monomer containing carbon, hydrogen, halogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
- C10M2213/043—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/0606—Perfluoro polymers used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
- Pyridine Compounds (AREA)
Abstract
Compounds formed of (per)fluoropolyether chains and end groups having a pyridine structure, with structural formula:
T1-CW1-O-R f-CW2-T2(I) wherein T1, T2, equal to or different from each other, have the following meanings:
- F, CF3, C2F5, (C2F4)C1:
- CH2-B-Y, CH (CF3) O-Y, wherein:
- B = O, S;
(see above formula) wherein R1, R2, R3, R4, equal to or different from each other, are H, F, C1-C8 linear or branched perfluoroalkyl, NO2, CN;
with the proviso that at least one of the two end groups T1, T2 is CH2-B-Y or CH(CF3)O-Y as above defined;
W1, W2, equal to or different from each other, are -F, -CF3;
Rf is a (per)fluoropolyoxyalkylene chain having a number average molecular weight from 400 to 10,000.
T1-CW1-O-R f-CW2-T2(I) wherein T1, T2, equal to or different from each other, have the following meanings:
- F, CF3, C2F5, (C2F4)C1:
- CH2-B-Y, CH (CF3) O-Y, wherein:
- B = O, S;
(see above formula) wherein R1, R2, R3, R4, equal to or different from each other, are H, F, C1-C8 linear or branched perfluoroalkyl, NO2, CN;
with the proviso that at least one of the two end groups T1, T2 is CH2-B-Y or CH(CF3)O-Y as above defined;
W1, W2, equal to or different from each other, are -F, -CF3;
Rf is a (per)fluoropolyoxyalkylene chain having a number average molecular weight from 400 to 10,000.
Description
Description of the industrial invention ir_ the name of:
SOLVAY SOLEXIS S.p.A., of Italian nationality, with head office in Milano, Via Turati, 12.
The present invention relates to stabilizing additives for lubricating oils and greases.
More specifically the invention relates to additives ca-pable to stabilize oils and greases having a perfluoropolyet-her structure towards Lewis acids, the process for their pre-paration and to oil and grease compositions having a perfluo-ropolyether structure comprising said additives.
It is known in the prior art that perfluoropolyethers have very good properties of chemical, thermal stability and are therefore used in many applications as lubricating oils or greases or hydraulic fluids. Among lubricants having a per-fluoropolyether structure, FOMBLIN~ commercialized by Solvay Solexis car be mentioned.
Particularly critical applications are those wherein lu-bricants having a perfluoropolyether structure are in the pre-sence of Lewis acids. It is known that Lewis acs_ds, as for example aluminum, iron, titanium, vanadium oxides or fluorides and others are catalysts of perfluoropolyether degradations, causing the complete lubricant decomposition.
The applications wherein lubricants come into contact (~F e787/031/EST;
SOLVAY SOLEXIS S.p.A., of Italian nationality, with head office in Milano, Via Turati, 12.
The present invention relates to stabilizing additives for lubricating oils and greases.
More specifically the invention relates to additives ca-pable to stabilize oils and greases having a perfluoropolyet-her structure towards Lewis acids, the process for their pre-paration and to oil and grease compositions having a perfluo-ropolyether structure comprising said additives.
It is known in the prior art that perfluoropolyethers have very good properties of chemical, thermal stability and are therefore used in many applications as lubricating oils or greases or hydraulic fluids. Among lubricants having a per-fluoropolyether structure, FOMBLIN~ commercialized by Solvay Solexis car be mentioned.
Particularly critical applications are those wherein lu-bricants having a perfluoropolyether structure are in the pre-sence of Lewis acids. It is known that Lewis acs_ds, as for example aluminum, iron, titanium, vanadium oxides or fluorides and others are catalysts of perfluoropolyether degradations, causing the complete lubricant decomposition.
The applications wherein lubricants come into contact (~F e787/031/EST;
with Lewis acids are for example the magnetic disc lubrication or the metal part lubrication in thermo-oxidative environment.
In the first case the Lewis acid is one of the disc consti-tuents; in thermo-oxidative envricnment the Lewis acid is' for-med in the lubricant utilization conditions.
European patent application No. 03008436 in the name of the Applicant describes stabilizing additives not containing phosphor, with a (per)fluoropolyether structure and having a-ryl terminals containing -N02 groups. According to this patent application the additives are used to stabilize perfluoro-polyether oils and greases in thermo-oxidative environment in the presence of metals. Tests carried out by the Applicant ha-ve shown that said additives have good performances in the presence of Lewis acids, however it would be desirable to further improve the fluid stability.
In USP 6,083,F>00 lubricants for magnetic discs comprising stabilizing compounds formed of chains constituted by repea-ting units - (CFZ) n-0-, wherein n is from 1 to 4 and having as end groups at least one amine group of -CH2NRR' type, wherein R and R' are alkyl groups, are described. The synthesis of these amines requires the use of trifluoromethyl sulphonyl chloride. It is an expensive reactant and requires the use of particular operating conditions, since it must be used in an-hydrous environment. From the industrial point of view said (AF c7&7/031/EST;
In the first case the Lewis acid is one of the disc consti-tuents; in thermo-oxidative envricnment the Lewis acid is' for-med in the lubricant utilization conditions.
European patent application No. 03008436 in the name of the Applicant describes stabilizing additives not containing phosphor, with a (per)fluoropolyether structure and having a-ryl terminals containing -N02 groups. According to this patent application the additives are used to stabilize perfluoro-polyether oils and greases in thermo-oxidative environment in the presence of metals. Tests carried out by the Applicant ha-ve shown that said additives have good performances in the presence of Lewis acids, however it would be desirable to further improve the fluid stability.
In USP 6,083,F>00 lubricants for magnetic discs comprising stabilizing compounds formed of chains constituted by repea-ting units - (CFZ) n-0-, wherein n is from 1 to 4 and having as end groups at least one amine group of -CH2NRR' type, wherein R and R' are alkyl groups, are described. The synthesis of these amines requires the use of trifluoromethyl sulphonyl chloride. It is an expensive reactant and requires the use of particular operating conditions, since it must be used in an-hydrous environment. From the industrial point of view said (AF c7&7/031/EST;
operating conditions make more complicated the synthesis pro-cess. Besides, tests carried out by the Applicant have shown that the compounds obtained according to this patent, used as additives of lubricants having a perfluoropolyether structure operating in the presence of Lewis acids, have good performan-ces; however it would be desirable to further improve the fluid stability.
The need was felt to have available additives for lubri-eating fluids having a perfluoropolyether basis, operating in the presence of Lewis acids, having the following combination of properties:
- improved stabilizing properties in the presence of Lewis acids, even at high temperatures, in comparison with the (per)fluoropolyether additives of the prior art;
- simplified synthesis prccess.
The Applicant has surprisingly and unexpectedly found ad-ditives having the above combination of properties..
An object of the present invention are compounds usable as stabilizing additives of perfluoropolyether fluids opera-ting in the presence of Lewis acids, said additives formed of (per)fluoropolyether chains and end groups having a pyridine structure, having the following structural formula:
T1-CW1-p-R f-CWZ-T2 ( I ) wherein (AF 2787/031/$ST) T1, T2, equal to or different from each other, have the following meanings:
- F. CFs. CzFs. (CzF4)C1;
- CHz-B-Y, CH (CF3) 0-Y, wherein:
- B = O, S;
T
N-wherein R~, Rz, R3, R4, equal to or different from each other are H, F, C1-Ca linear or bran-ched perfluoroalkyl, NO2, CN, preferably H
and/or C1-CB linear or branched perf:Luoroalkyl;
with the proviso that at least one of the two end groups Tz, T2 is CHZ-B-Y or CH (CF3) O-Y as above defined;
wi. Wz. equal to or different from each other, are -F, _CFs;
- Rf is a (per)fluoropolyoxyalkylene chain formed of one or more repeating units, statistically distributed in the chain, having the fcllowing structure:
(CFXO) , (CFzCFzO) , (CF2CF2CF20) , (CFzCFZCFZCF20) , (CR5R6CFZCF20) , (CF (CF3) CF20) , (CF2CF (CF3) 0) , (AF 2787/031/EST) wherein X = F , CF3; R5 and R6, equal to or different from each other, are selected among H, C1, perfluoroalkyl from 1 to 4 carbon atoms;
the number average molecular weight of Rf beei.ng from 400 to 10,000, preferably from 800 to 5,000.
The {per)fluoropolyether chain Rf is preferably selected from the follcwing structures:
(A) -(CF2CF(CF3)0)a(CFXO)b- or - (CF2CF (CF3) 0) a (CFXO) ~-CF2 (R' p) CF2-O- (CF2CF (CF3) O) a (CFXO) ~,-wherein R'f is a fluoroalkylene group from 1 to 4 C
atoms; X is F or CF3; a and b are integers such that the number average molecular weight is within the above ran-ge; a/b is between 10 and 100;
{B) - (CF2CF20) c (CF20) d (CF2 (CF2) z0) h-wherein c, d and h are integers such that the number average molecular weight is within the above range; c/d is between 0.1 and 10; h/{c+d) is between 0 and 0.05, z is 2 or 3; h can also be equal to 0;
(C) - (CF2CF (CF3) O) a (CF2CF20) f (CFXO) ~-wherein X is F or CF3; e, f, g are integers such that the number average molecular weight is within the above ran-ge; e/ (f+g) is between 0. 1 and 10; f/g is between 2 and 10;
(D) - (CF2 {CF2) ZO) 5-(AF 2787/031/EST) wherein s is an integer such as to give the above molecu-lar weight, z has the already defined meaning;
(E) - (CR5R6CF2CF20) ~.- or - (CRSR6CFZCF20) p.-R' f-O-- (CR5R6CFZCF20) q.-wherein RS and R6 are equal to or different from each other and selected among H, C1 or perfluoroalkyl from 1 to 4 C atoms; R'f is a fluoroalkylene group from 1 to 4 C
atoms; j', p' and q' are integers such as to have a mole-cular weight as that above mentioned;
(F) - (CF (CF3) CF20) ~ or - (CF (CF3) CFO) ~-R' f-0- (CF (CF3) CFzO) J,.-wherein R'f is a fluoroalkylene group from 1 to 4 C
atoms; j" being an integer such as to give the above mo-lecular weight.
Preferably the perfluoropolyether Rf structures in the compounds of formula (I) are selected from the structures (A) and (B) .
The preferred compounds of formula (I) are those wherein the (per)fluoropolyether chains are linked by an ether func-tion to the carbon atom in alpha position with respect to the nitrogen atom cf the pyridine ring Y.
The Applicant has surprisingly found that the compounds of the inven~ion can be used as additives of perfluorinated lubricants, as, for example, perfluaropolyether-based oils or (AF 2787/C31/EST) greases, supplying stabilizing performances, towards the Lewis acids, even at a high temperature, improved with respect to those obtained-with known additives having a (per)fluoro-polyether chain, as for example those described in USP
6, 083, 600.
It is for example well known that perfluoropolyethers ha-ving the structure B) are used in the lubrication even at tem-peratures close to 200°C. In the presence of Lewis acids said perfluoropolyethers decompose quite completely after 24 hours at the temperature of 250°C_ It has been surprisingly found that the addition. of the additives of the present invention allows to use said fluids even at higher temperatures, higher than 200°C, for example 220°C-230°C. In fact tests carried out at 250°C have shown that the oil remains stable for at least 24 hours since the weight loss is very low. The additives of the prior art, for example, with propylamine end groups show a decomposition which is about 1.5 times higher; for the additi-ves with nitroaryl end groups the loss is about 2.5 times. The invention results are quite surprising and unexpected since there is no suggestion in the prior art that additives with a perfluoropolyether structure having pyridine end groups had improved stabilizing properties of the perfluoropolyether fluids.
The compounds object of the present invention are viscous (AF 2787/031/EST) transparent and odourless liquids.
A further object of the present invention are lubricating compositions comprising:
- an oil or a grease having a perfluoropolyether structure;
- from 0.050 to l0a by weight, preferably from 0.1% to 50 by weight on the total of the composition, of compounds of formula (I) of the present invention;
the composition being substantially formed of the ail or grea-se.
The perfluoropolyethers usable as oils or as a basis for the grease preparation are described hereinafter. Examples of perfluoropolyether oils are those having structures belonging to the following classes:
(1) E-O-(CF(CF3)CF20)m~ (CFXO)n~-E' wherein:
X is equal to F or CF3;
E and E', equal to or different from each other, are se-lected among CF3, CZFS or C3F~;
m' and n' are integers such that the m'/n' :ratio is in the range 20-1,000 and the product viscosity is in the range 10-4,000 cSt; the various units are statistically distributed along the chain.
These products can be obtained by perfluoropropene pho-tooxidation as described in GB 1,104,432, and by subse-(AF 2787/031/EST) quent conversion of the end groups as described in GB
l, 226, 566.
(2 ) C3F70- (CF (CF3) CF20) o~-D
wherein:
D is equal to -CZFJ or -C3F-,;
o' is an integer such that the product viscosity is wi-thin the above range.
These products can be prepared by ionic oligomerization of the perfluoropropylenoxide and subsequent treatment with fluorine as described in USP 3,242,218.
{3) {C3F7O-(CF(CF3)CF20)P.-CF(CF3)-}2 wherein:
p' is an integer such that the compound viscosity is wi-thin the above range.
These products can be obtained by ionic telomerization of the perfluoropropylenoxide and subsequent photochemical dimerization as reported in USP 3,214,478.
{4) E-O-{CF {CF3) CF20) q~ (C2F4O) r~ (CFX) S.-E
wherein:
X is equal to F or CF3;
E and E' , equal to or different from each other, are as above;
q', r' and s' are integers and can also have t:he 0 value, and such that the product viscosity is within the above (AE' 2787/031/EST) range.
These products are obtained by photooxidatior_ of a mixtu-re of C3F6.and C2F4 and subsequent treatment with fluorine as described in USP 3,665,041.
The need was felt to have available additives for lubri-eating fluids having a perfluoropolyether basis, operating in the presence of Lewis acids, having the following combination of properties:
- improved stabilizing properties in the presence of Lewis acids, even at high temperatures, in comparison with the (per)fluoropolyether additives of the prior art;
- simplified synthesis prccess.
The Applicant has surprisingly and unexpectedly found ad-ditives having the above combination of properties..
An object of the present invention are compounds usable as stabilizing additives of perfluoropolyether fluids opera-ting in the presence of Lewis acids, said additives formed of (per)fluoropolyether chains and end groups having a pyridine structure, having the following structural formula:
T1-CW1-p-R f-CWZ-T2 ( I ) wherein (AF 2787/031/$ST) T1, T2, equal to or different from each other, have the following meanings:
- F. CFs. CzFs. (CzF4)C1;
- CHz-B-Y, CH (CF3) 0-Y, wherein:
- B = O, S;
T
N-wherein R~, Rz, R3, R4, equal to or different from each other are H, F, C1-Ca linear or bran-ched perfluoroalkyl, NO2, CN, preferably H
and/or C1-CB linear or branched perf:Luoroalkyl;
with the proviso that at least one of the two end groups Tz, T2 is CHZ-B-Y or CH (CF3) O-Y as above defined;
wi. Wz. equal to or different from each other, are -F, _CFs;
- Rf is a (per)fluoropolyoxyalkylene chain formed of one or more repeating units, statistically distributed in the chain, having the fcllowing structure:
(CFXO) , (CFzCFzO) , (CF2CF2CF20) , (CFzCFZCFZCF20) , (CR5R6CFZCF20) , (CF (CF3) CF20) , (CF2CF (CF3) 0) , (AF 2787/031/EST) wherein X = F , CF3; R5 and R6, equal to or different from each other, are selected among H, C1, perfluoroalkyl from 1 to 4 carbon atoms;
the number average molecular weight of Rf beei.ng from 400 to 10,000, preferably from 800 to 5,000.
The {per)fluoropolyether chain Rf is preferably selected from the follcwing structures:
(A) -(CF2CF(CF3)0)a(CFXO)b- or - (CF2CF (CF3) 0) a (CFXO) ~-CF2 (R' p) CF2-O- (CF2CF (CF3) O) a (CFXO) ~,-wherein R'f is a fluoroalkylene group from 1 to 4 C
atoms; X is F or CF3; a and b are integers such that the number average molecular weight is within the above ran-ge; a/b is between 10 and 100;
{B) - (CF2CF20) c (CF20) d (CF2 (CF2) z0) h-wherein c, d and h are integers such that the number average molecular weight is within the above range; c/d is between 0.1 and 10; h/{c+d) is between 0 and 0.05, z is 2 or 3; h can also be equal to 0;
(C) - (CF2CF (CF3) O) a (CF2CF20) f (CFXO) ~-wherein X is F or CF3; e, f, g are integers such that the number average molecular weight is within the above ran-ge; e/ (f+g) is between 0. 1 and 10; f/g is between 2 and 10;
(D) - (CF2 {CF2) ZO) 5-(AF 2787/031/EST) wherein s is an integer such as to give the above molecu-lar weight, z has the already defined meaning;
(E) - (CR5R6CF2CF20) ~.- or - (CRSR6CFZCF20) p.-R' f-O-- (CR5R6CFZCF20) q.-wherein RS and R6 are equal to or different from each other and selected among H, C1 or perfluoroalkyl from 1 to 4 C atoms; R'f is a fluoroalkylene group from 1 to 4 C
atoms; j', p' and q' are integers such as to have a mole-cular weight as that above mentioned;
(F) - (CF (CF3) CF20) ~ or - (CF (CF3) CFO) ~-R' f-0- (CF (CF3) CFzO) J,.-wherein R'f is a fluoroalkylene group from 1 to 4 C
atoms; j" being an integer such as to give the above mo-lecular weight.
Preferably the perfluoropolyether Rf structures in the compounds of formula (I) are selected from the structures (A) and (B) .
The preferred compounds of formula (I) are those wherein the (per)fluoropolyether chains are linked by an ether func-tion to the carbon atom in alpha position with respect to the nitrogen atom cf the pyridine ring Y.
The Applicant has surprisingly found that the compounds of the inven~ion can be used as additives of perfluorinated lubricants, as, for example, perfluaropolyether-based oils or (AF 2787/C31/EST) greases, supplying stabilizing performances, towards the Lewis acids, even at a high temperature, improved with respect to those obtained-with known additives having a (per)fluoro-polyether chain, as for example those described in USP
6, 083, 600.
It is for example well known that perfluoropolyethers ha-ving the structure B) are used in the lubrication even at tem-peratures close to 200°C. In the presence of Lewis acids said perfluoropolyethers decompose quite completely after 24 hours at the temperature of 250°C_ It has been surprisingly found that the addition. of the additives of the present invention allows to use said fluids even at higher temperatures, higher than 200°C, for example 220°C-230°C. In fact tests carried out at 250°C have shown that the oil remains stable for at least 24 hours since the weight loss is very low. The additives of the prior art, for example, with propylamine end groups show a decomposition which is about 1.5 times higher; for the additi-ves with nitroaryl end groups the loss is about 2.5 times. The invention results are quite surprising and unexpected since there is no suggestion in the prior art that additives with a perfluoropolyether structure having pyridine end groups had improved stabilizing properties of the perfluoropolyether fluids.
The compounds object of the present invention are viscous (AF 2787/031/EST) transparent and odourless liquids.
A further object of the present invention are lubricating compositions comprising:
- an oil or a grease having a perfluoropolyether structure;
- from 0.050 to l0a by weight, preferably from 0.1% to 50 by weight on the total of the composition, of compounds of formula (I) of the present invention;
the composition being substantially formed of the ail or grea-se.
The perfluoropolyethers usable as oils or as a basis for the grease preparation are described hereinafter. Examples of perfluoropolyether oils are those having structures belonging to the following classes:
(1) E-O-(CF(CF3)CF20)m~ (CFXO)n~-E' wherein:
X is equal to F or CF3;
E and E', equal to or different from each other, are se-lected among CF3, CZFS or C3F~;
m' and n' are integers such that the m'/n' :ratio is in the range 20-1,000 and the product viscosity is in the range 10-4,000 cSt; the various units are statistically distributed along the chain.
These products can be obtained by perfluoropropene pho-tooxidation as described in GB 1,104,432, and by subse-(AF 2787/031/EST) quent conversion of the end groups as described in GB
l, 226, 566.
(2 ) C3F70- (CF (CF3) CF20) o~-D
wherein:
D is equal to -CZFJ or -C3F-,;
o' is an integer such that the product viscosity is wi-thin the above range.
These products can be prepared by ionic oligomerization of the perfluoropropylenoxide and subsequent treatment with fluorine as described in USP 3,242,218.
{3) {C3F7O-(CF(CF3)CF20)P.-CF(CF3)-}2 wherein:
p' is an integer such that the compound viscosity is wi-thin the above range.
These products can be obtained by ionic telomerization of the perfluoropropylenoxide and subsequent photochemical dimerization as reported in USP 3,214,478.
{4) E-O-{CF {CF3) CF20) q~ (C2F4O) r~ (CFX) S.-E
wherein:
X is equal to F or CF3;
E and E' , equal to or different from each other, are as above;
q', r' and s' are integers and can also have t:he 0 value, and such that the product viscosity is within the above (AE' 2787/031/EST) range.
These products are obtained by photooxidatior_ of a mixtu-re of C3F6.and C2F4 and subsequent treatment with fluorine as described in USP 3,665,041.
(5) E_0_ (C2F40) t, (CFzO)u~_E~
wherein:
E and E' , equal to or different from each other, are as above;
t' and u' are integers such that the t'/u' ratio is in the range 0.1-5 and the product viscosity is within the above range_ These products are obtained by photooxidation of C2 F4 as reported in USP 3,715,378 and subsequent treatment with fluorine as described in USP 3,665,041.
( 6) E-0- (CF2CF2CF20) ~~-E' wherein:
E and E' , equal to or different from each other, are as above;
v' is a number such that the product viscosity is within the above range.
These products are obtained as described in EP 148,482.
D_0_ (CF2CF20) Z,_D
wherein:
D and D', equal to or different from each other, are se-(AF 2787/031/EST) lected between C2F5 or C3F7;
z' i s an integer such that the product viscosity is wi-thin the above range.
These products can be obtained as reported in USP
4,523,039.
The perfluoropolyether of the classes from (1) to (7) are liquids having a very low vapour pressure value and generally have a viscosity measured at 20°C from 30 to 100,000 c5t, pre-ferably from 100 to 2,000 cSt.
The preferred perfluoropolyether oils are those of the classes (1), (4), (5) and are available on the market with the trademark FOMBLIN° sold by Solway Solexis.
The invention formulations can also contain other additi-ves commonly used in formulations of lubricants hawing a per-fluoropolyether structure as for example anti-rust, anti-oxidant or anti-wear additives.
Furthermore, in the case of lubricating greases, the for-mutations contain, besides the perfluoropolyether oil belon-ging to one or more of the above mentioned classes, as essen-tial component, a thickener, in the known amounts of the prior art, as for example PTFE, sodium terephthalamate, calcium or lithium soaps, polyurea, etc. Other additives generally con-tamed in the lubricating grease compositions are the disper-sants such as for example surfactants, in particular non io-(AF 2787/031/ESTj nic, and preferably having a perfluoropolyether or perfluo-roalkyl structure; talc or inorganic fillers. Besides the lu-bricating grease compcsitions according to the present inven-tien can also contain other additives commonly used in grease formulations, such for example anti-rust, anti-oxidant or an-ti-wear additives.
The amounts of said additives are those generally used for this kind of compositions.
The amounts of oil or grease in the invention composition are those commonly used in lubricating compositions based on oils or greases as above defined.
A further object of the present invention is a process to obtain the compounds of formula (I) comprising the following steps:
a) preparation of an alcoholate or thiolate by reaction of a compound having a (per)fluoropolyoxyalkylene structure of formula:
T' 1-CWi-0-R f-CLVz-T' 2 ( I I ) wherein:
R~, W1 and W2 have the above meanings;
T' i and T ° 2, equal to or different from each other, represent an end group selected from the following:
CH20H, CHZSH, CH (OH) CF3, F, CF3, C2 F5, (CZF4) C1;
with the proviso that at least one~of the two end (AF 2787/D31/EST) groups T' 1 and/or T' 2 is equal to CH20H, CH2SH or CH (OH) CF3;
with an organic ar inorganic base, in organic solvent inert under the reaction conditions;
b) reaction of the alcoholate or thiolate obtained in step a) with a pyridine compound of formula R2 Rs Q
r2 ~R4 N
(ITI) wherein R1, R2, R3, R4 have the above meaning, Q is halogen selected from Cl, Br, I, wherein the ratio of the equivalents between the alcoho-late or thiolate function of the (per)fluorinated chain and the pyridine compound ( III ) is from 1 to 0 . 5, prefe-rably from 0.8 to 0.6, in an organic solvent inert under the reaction conditions, at a temperature in the range 20°C- 100°C, preferably 40°C-80°C;
c) isolation of the reaction product.
Steps a) + b) can be simultaneously carried out, prefe-rably in the presence of a phase transfer agent; alternatively they can be carried out in sequence.
The phase transfer agent is preferably a phosphonium or a quaternary ammonium salt known in the prior art, for example (AF 2787/031/EST) tetrabutylammonium hydroxide, tetramethylammonium chloride.
When the steps a) + b) take place simultaneously, the or-ganic solvent is preferably selected from hydrogenated sol-vents, as for example acetonitrile, ch~_orobenzene, toluene, xylene, or fluorinated or hydrofluorinated solvents, having boiling point in the range 20°C-150°C, preferably 40°C-100°C.
The ratic by weight between the solvent and the (per)fluorinated alcohol or thiol is preferably from 0.5 to 10, more preferably from 2 to 5.
The bases are preferably K2C03 or solid NazC03,. aqueous solutions of NaOH or KOI~ at a concentration .from 20o to 60%
w/w, preferably from 30% to 50o w/w.
The ratio between the base equivalents and the (per)fluorinated alcohol or thiol equivalents ranges from 2 to 10.
The equivalents of the phase transfer agent, when used, are in a ratio with the equivalents of the (per)fluorinated alcohol or thiof from 0.01 to 0.1.
The reacticn times are function of the reaction tempera-ture and generally comprised between 4 and 24 hours. For exam-ple, when the reaction temperature is 80°C: the reaction time is of about 6 hours.
When steps a) + b) are carried out in sequence, the com-pound of structure (II) is reacted in the first step with an (AF 2787/031/EST) organic or inorganic base, selected for example among potas-sium terbutylate, OOH, NaH.
The ratio between the base equivalents and those of the compound of structure (II) ranges from 1.2 to 2, preferably from 1.2 to 1.5; the reaction solvent is preferably selected from terbutyl aicohoi, acetonitrile, diglyme, DMF.
In the second step of the process the obtained (per)fluoropolyether alcoholate or thiolai=a is reacted with a compound of formula (III) under the above conditions.
As said, the additives having a (per)fluoropolyether structure according to the present invention allow to obtain formulations of (per)fluoropolyether oils and greases having an improved stability to Lewis acids in comparison with the same formulations containing the same amount of (per)fluoropolyether additives of the prior art.
The present invention will be better illustrated by the following Examples, having a merely illustrative and not limi-tative purpose of the invention.
EXAMPLES
Stability test to Lewis acids fcr oils The determiantion of the stability of the oils to be te-sted to Lewis acids in the presence of the additives according to the presenø~ invention has been carried out as follows.
5 grams of the fluid to be tested, optionally containing (AF 2787/031/EST) the additive at the concentration indicated in the Examples, and 0.10 g of A1 F3 are introduced in a glass test tube (about cc). The test tube is weighed and closed with a screw plug having a hole in the middle on which a 30 cm PT FE small pipe is fixed which conveys possible decomposition products in, a NaOH solution (0,1 N) contained in a collection cylinder. The test tube is then heated to 250°C for 24 hours. At the end the test tube is ccoled and weighed. The test. result is expressed in per cent weight loss of the starting fluid.
Stabilitv'test to Lewis acids for ctreases 50 g of grease to be tested, optionally containing the additive at the concentration indicated in the Examples, are additived with 5o by weight of AlF3 and deposited, by a stra-tifying knife, in a glass capsule having a diameter of 95 mm, so as to cover the whole exposed surface. The capsule is pla-ced in a drier for 30', then weighed and placed in a stove at 250°C. After 4 hours the capsule is taken off from the oven and let cool in a drier. The capsule is then weighed again and it is evaluated the per cent weight loss with respect to the initial weight. The test result is therefore expressed in percent weight loss with respect to the initial weight.
(AE 2787/031/EST) nvTennr c Preparation of the derivative of formula (IV) ~i N ~OCH2CF20(CF2CF20)c(CF20)dCF2CMz0 ~N
(IV) having a number average molecular weight = 2388.
140 g of tert-butyl alcchol and 14 g (0.125 moles) of po-tassium terbutylate are introduced in a 1,000 ml glass reactor equipped with mechanical stirrer, thermometer and condenser.
Then 100 g (0.095 eq) of HOCHzCF20(Cf2CFz0)~(CF20)dCF2CH20H
(EW - 1049) wherein c/d = 1 are introduced under stirring at room temperature. The reaction mixture is left under stirring at room temperature for about 30 minutes, then 17.3 g (0.095 moles) of 2-chloro-3-trifluoromethyl pyridine are fed into the reactor. The so obtained mixture is heated to 70°C and kept under stirring for about 6 hours. After cooling 500 g of demi-neralized water are added. Then the phases are let separate and the heavy organic phase is recovered and washed two times with 500 g of demineralized water. The organic phase is then anydrified by s~.ripping at 100°C at a residual pressure of 102 mbar for about 4 hours, and successively filtered on PTFE
0.2 um filter. 106 g of product are obtained wherein the con-(AF 278'7/031/EST) 1$
version of alcoholic groups into ether groups is 93°s. The IR
and NMR (1H, 1~F and 13C) analyses confirm the structure of the above indicated product (IV}.
T'.~VTTAT~T TT '-7 Preparation of the derivative (V) having pyridine end groups \ /
OCH2CF20~CFZCF20x(CF20xICF2CHl20 N
(V}
having number average molecular weight 4202.
Example 1 is repeated but using the following reactants in the indicated amounts: tert-butyl alcohol 140 g; potassium terbutylate 7.5 g (0.067 moles);
HOCH2CF20 (CF2CF20) C (CF20) dCF2CH20H (EW = 1956) wherein c/d = 0. 8, 100 g (0.051 eq); 2-chloro-3-trifluoromethyl pyridine 10.21 g (0.056 moles).
104 g of product are obtained wherein the conversion of alcohol groups into ether groups is 85 0 . 'The I:R and NMR (1H, 1~F a 13C) ar_alyses confirm the structure of the above indica-ted product.
L''YTMDT L~
The stability test to Lewis acids for oils is carried (AF 2787/031/EST) out, by using 5 g of Fomblir_~ Z25 oil, having number average molecular weight 10,000, additived with 0.05 g of the com-pound (IV) of the Example ''.
After 24 hcurs a loss by weight of the fluid equal to 0.180 is determined. The Example is summarized ir_ Table 1.
The stability test to Lewis acids for oils is carried out by using 5 g of Fomblin~ Z25 oil, having number average molecular weight of 10,000, additived with 0.05 g of the com-pound (V) of the Example 2.
After 24 hours a fluid weight loss equal to 0.16% is de-termined. The Example is summarized in Table 1.
EXAMPZE 5 (comparative Example 3 is repeated, but in absence of the invention additive.
The fluid results completely decomposed after 5 hours from the beginning of the test. The Example is summarized in Table 1.
Example 3 is repeated, but by using an oil having number average molecular weight 13.000 (Fomblin~ ?60).
After 24 hours a weight loss of the fluid equal to 0.16%
is determined. The Example is summarized in Table 1.
(AF 2787/031/EST) zo EXAMPLE 7 (comparative) Example 6 is repeated without the invention additive.
After 24 hours a weight loss of the fluid equal to 52.2 is determined. The Example is summarized in Table 1.
EXAMPLE 8 (comparative) Example 6 is repeated, but by using' 0.05 g of the fol-lowing additive of formula (VI) described in USP 6,083,600:
( CH3CH2CH2 ) ~-N-CH~CF20 ( CF2CF20 ) ~ ( CF2C ) dCFzCH2-N- ( C:~i2CH2CH3 ) ~
ha-ving number average molecular weight 2000.
24 hours elapsed, a weight loss of the fluid equal to 0.25% is determined. The Example is summa:eized in Table y.
EXAMPLE 9 (comparative) Example ? is repeated but by using 1° of the stabilizing additive having the following formula (VIl-):
p2N ~ ~ OCHZCF2(OCFzCF2)m(OCFZ)nOCF2CHz0 S ~ N02 wherein the number average molecular weight of the (per)fluoropolyether chain is 1966 and m/n - 1.2, prepared according to the Example l of European patent application No.
03008436.
24 hours elapsed, a weight loss of the fluid equal to 0.420 is determined. The Example is summarized in Table 1.
(AF 2787/031/EST) A grease is prepared by mixing 70o by weight of Fomblin~
M30 having molecular weight 9,800, with 30o by weight of PTFE. The grease is additived with la by weight of the addi-tive prepared according to the Example ? and then subjected to the stability test to Lewis acids for greases. At the end of the test a per cent weight loss of 1.6°s is determined. The Example is summarized in Table 1.
EXAMPLE 11 (comparative) Example 10 is repeated, but in absence of the invention additive. At the end of the test, a per cent weight loss of 66o is detrmined. The Example is summarized in Table ~.
(AF 2787/031/EST) i '~5.r, -~
a~ a~ .~ ~ ..c a-~
cn N 3 b' -r-Ico ~O 4) ~ N ~.WN
(U .;-F H l0 r-~~--I4-Ir-i N V~
O ~ ~ W ?i Q3 N lQ
O O O {.t~O O
U (l~ O
o t~ U7 U
S- l 'Z~
U ~.F
O
r-i _ ',-i O
O ~ ~ ~ . '-i togM N
4-I _.
if r-i I i Cp~ I
-O -~ N x O x ~ ~ x ~ o N '~'~'~,~ ~ ~ x ~ N
.~ 45 paW
N r-i 'ZS _ _ r~W _ ~ ~C _ H H
_ H
U1 -I-~~-I
r-i N ~S 1-~
tI$
_ U) ~
fa _,~1-) N
E-~ bi N _ _ ~ _r-S+-~ O N
O O
'~ ~ O J~
_,_.F ~ O O
O
U ~ .~ O _ _ O _ .. Cxd ~ O M O
o x r~ r-I ri E-1 .,~ ~.1 3 3 ow U U N ~
~ -I-~ ~, N ~ N
f/~ ~ ~ ~ O
~ ~o O N N N
"-i H
W
a r-., ~ ..
o ~ +~'-~' ua N W w CL, p +~ d) U W
~, o ow +~ ~ t~ o r v >, x -i .5.~ -~ -~~-1t1~ x r7 cr ~ ~p t0 'Z3Ul W
r +.~ ~ 'z3O
U7 -~-Iitsr-i ~ t~-m 61 H
(AF' 2787/03?/EST;
wherein:
E and E' , equal to or different from each other, are as above;
t' and u' are integers such that the t'/u' ratio is in the range 0.1-5 and the product viscosity is within the above range_ These products are obtained by photooxidation of C2 F4 as reported in USP 3,715,378 and subsequent treatment with fluorine as described in USP 3,665,041.
( 6) E-0- (CF2CF2CF20) ~~-E' wherein:
E and E' , equal to or different from each other, are as above;
v' is a number such that the product viscosity is within the above range.
These products are obtained as described in EP 148,482.
D_0_ (CF2CF20) Z,_D
wherein:
D and D', equal to or different from each other, are se-(AF 2787/031/EST) lected between C2F5 or C3F7;
z' i s an integer such that the product viscosity is wi-thin the above range.
These products can be obtained as reported in USP
4,523,039.
The perfluoropolyether of the classes from (1) to (7) are liquids having a very low vapour pressure value and generally have a viscosity measured at 20°C from 30 to 100,000 c5t, pre-ferably from 100 to 2,000 cSt.
The preferred perfluoropolyether oils are those of the classes (1), (4), (5) and are available on the market with the trademark FOMBLIN° sold by Solway Solexis.
The invention formulations can also contain other additi-ves commonly used in formulations of lubricants hawing a per-fluoropolyether structure as for example anti-rust, anti-oxidant or anti-wear additives.
Furthermore, in the case of lubricating greases, the for-mutations contain, besides the perfluoropolyether oil belon-ging to one or more of the above mentioned classes, as essen-tial component, a thickener, in the known amounts of the prior art, as for example PTFE, sodium terephthalamate, calcium or lithium soaps, polyurea, etc. Other additives generally con-tamed in the lubricating grease compositions are the disper-sants such as for example surfactants, in particular non io-(AF 2787/031/ESTj nic, and preferably having a perfluoropolyether or perfluo-roalkyl structure; talc or inorganic fillers. Besides the lu-bricating grease compcsitions according to the present inven-tien can also contain other additives commonly used in grease formulations, such for example anti-rust, anti-oxidant or an-ti-wear additives.
The amounts of said additives are those generally used for this kind of compositions.
The amounts of oil or grease in the invention composition are those commonly used in lubricating compositions based on oils or greases as above defined.
A further object of the present invention is a process to obtain the compounds of formula (I) comprising the following steps:
a) preparation of an alcoholate or thiolate by reaction of a compound having a (per)fluoropolyoxyalkylene structure of formula:
T' 1-CWi-0-R f-CLVz-T' 2 ( I I ) wherein:
R~, W1 and W2 have the above meanings;
T' i and T ° 2, equal to or different from each other, represent an end group selected from the following:
CH20H, CHZSH, CH (OH) CF3, F, CF3, C2 F5, (CZF4) C1;
with the proviso that at least one~of the two end (AF 2787/D31/EST) groups T' 1 and/or T' 2 is equal to CH20H, CH2SH or CH (OH) CF3;
with an organic ar inorganic base, in organic solvent inert under the reaction conditions;
b) reaction of the alcoholate or thiolate obtained in step a) with a pyridine compound of formula R2 Rs Q
r2 ~R4 N
(ITI) wherein R1, R2, R3, R4 have the above meaning, Q is halogen selected from Cl, Br, I, wherein the ratio of the equivalents between the alcoho-late or thiolate function of the (per)fluorinated chain and the pyridine compound ( III ) is from 1 to 0 . 5, prefe-rably from 0.8 to 0.6, in an organic solvent inert under the reaction conditions, at a temperature in the range 20°C- 100°C, preferably 40°C-80°C;
c) isolation of the reaction product.
Steps a) + b) can be simultaneously carried out, prefe-rably in the presence of a phase transfer agent; alternatively they can be carried out in sequence.
The phase transfer agent is preferably a phosphonium or a quaternary ammonium salt known in the prior art, for example (AF 2787/031/EST) tetrabutylammonium hydroxide, tetramethylammonium chloride.
When the steps a) + b) take place simultaneously, the or-ganic solvent is preferably selected from hydrogenated sol-vents, as for example acetonitrile, ch~_orobenzene, toluene, xylene, or fluorinated or hydrofluorinated solvents, having boiling point in the range 20°C-150°C, preferably 40°C-100°C.
The ratic by weight between the solvent and the (per)fluorinated alcohol or thiol is preferably from 0.5 to 10, more preferably from 2 to 5.
The bases are preferably K2C03 or solid NazC03,. aqueous solutions of NaOH or KOI~ at a concentration .from 20o to 60%
w/w, preferably from 30% to 50o w/w.
The ratio between the base equivalents and the (per)fluorinated alcohol or thiol equivalents ranges from 2 to 10.
The equivalents of the phase transfer agent, when used, are in a ratio with the equivalents of the (per)fluorinated alcohol or thiof from 0.01 to 0.1.
The reacticn times are function of the reaction tempera-ture and generally comprised between 4 and 24 hours. For exam-ple, when the reaction temperature is 80°C: the reaction time is of about 6 hours.
When steps a) + b) are carried out in sequence, the com-pound of structure (II) is reacted in the first step with an (AF 2787/031/EST) organic or inorganic base, selected for example among potas-sium terbutylate, OOH, NaH.
The ratio between the base equivalents and those of the compound of structure (II) ranges from 1.2 to 2, preferably from 1.2 to 1.5; the reaction solvent is preferably selected from terbutyl aicohoi, acetonitrile, diglyme, DMF.
In the second step of the process the obtained (per)fluoropolyether alcoholate or thiolai=a is reacted with a compound of formula (III) under the above conditions.
As said, the additives having a (per)fluoropolyether structure according to the present invention allow to obtain formulations of (per)fluoropolyether oils and greases having an improved stability to Lewis acids in comparison with the same formulations containing the same amount of (per)fluoropolyether additives of the prior art.
The present invention will be better illustrated by the following Examples, having a merely illustrative and not limi-tative purpose of the invention.
EXAMPLES
Stability test to Lewis acids fcr oils The determiantion of the stability of the oils to be te-sted to Lewis acids in the presence of the additives according to the presenø~ invention has been carried out as follows.
5 grams of the fluid to be tested, optionally containing (AF 2787/031/EST) the additive at the concentration indicated in the Examples, and 0.10 g of A1 F3 are introduced in a glass test tube (about cc). The test tube is weighed and closed with a screw plug having a hole in the middle on which a 30 cm PT FE small pipe is fixed which conveys possible decomposition products in, a NaOH solution (0,1 N) contained in a collection cylinder. The test tube is then heated to 250°C for 24 hours. At the end the test tube is ccoled and weighed. The test. result is expressed in per cent weight loss of the starting fluid.
Stabilitv'test to Lewis acids for ctreases 50 g of grease to be tested, optionally containing the additive at the concentration indicated in the Examples, are additived with 5o by weight of AlF3 and deposited, by a stra-tifying knife, in a glass capsule having a diameter of 95 mm, so as to cover the whole exposed surface. The capsule is pla-ced in a drier for 30', then weighed and placed in a stove at 250°C. After 4 hours the capsule is taken off from the oven and let cool in a drier. The capsule is then weighed again and it is evaluated the per cent weight loss with respect to the initial weight. The test result is therefore expressed in percent weight loss with respect to the initial weight.
(AE 2787/031/EST) nvTennr c Preparation of the derivative of formula (IV) ~i N ~OCH2CF20(CF2CF20)c(CF20)dCF2CMz0 ~N
(IV) having a number average molecular weight = 2388.
140 g of tert-butyl alcchol and 14 g (0.125 moles) of po-tassium terbutylate are introduced in a 1,000 ml glass reactor equipped with mechanical stirrer, thermometer and condenser.
Then 100 g (0.095 eq) of HOCHzCF20(Cf2CFz0)~(CF20)dCF2CH20H
(EW - 1049) wherein c/d = 1 are introduced under stirring at room temperature. The reaction mixture is left under stirring at room temperature for about 30 minutes, then 17.3 g (0.095 moles) of 2-chloro-3-trifluoromethyl pyridine are fed into the reactor. The so obtained mixture is heated to 70°C and kept under stirring for about 6 hours. After cooling 500 g of demi-neralized water are added. Then the phases are let separate and the heavy organic phase is recovered and washed two times with 500 g of demineralized water. The organic phase is then anydrified by s~.ripping at 100°C at a residual pressure of 102 mbar for about 4 hours, and successively filtered on PTFE
0.2 um filter. 106 g of product are obtained wherein the con-(AF 278'7/031/EST) 1$
version of alcoholic groups into ether groups is 93°s. The IR
and NMR (1H, 1~F and 13C) analyses confirm the structure of the above indicated product (IV}.
T'.~VTTAT~T TT '-7 Preparation of the derivative (V) having pyridine end groups \ /
OCH2CF20~CFZCF20x(CF20xICF2CHl20 N
(V}
having number average molecular weight 4202.
Example 1 is repeated but using the following reactants in the indicated amounts: tert-butyl alcohol 140 g; potassium terbutylate 7.5 g (0.067 moles);
HOCH2CF20 (CF2CF20) C (CF20) dCF2CH20H (EW = 1956) wherein c/d = 0. 8, 100 g (0.051 eq); 2-chloro-3-trifluoromethyl pyridine 10.21 g (0.056 moles).
104 g of product are obtained wherein the conversion of alcohol groups into ether groups is 85 0 . 'The I:R and NMR (1H, 1~F a 13C) ar_alyses confirm the structure of the above indica-ted product.
L''YTMDT L~
The stability test to Lewis acids for oils is carried (AF 2787/031/EST) out, by using 5 g of Fomblir_~ Z25 oil, having number average molecular weight 10,000, additived with 0.05 g of the com-pound (IV) of the Example ''.
After 24 hcurs a loss by weight of the fluid equal to 0.180 is determined. The Example is summarized ir_ Table 1.
The stability test to Lewis acids for oils is carried out by using 5 g of Fomblin~ Z25 oil, having number average molecular weight of 10,000, additived with 0.05 g of the com-pound (V) of the Example 2.
After 24 hours a fluid weight loss equal to 0.16% is de-termined. The Example is summarized in Table 1.
EXAMPZE 5 (comparative Example 3 is repeated, but in absence of the invention additive.
The fluid results completely decomposed after 5 hours from the beginning of the test. The Example is summarized in Table 1.
Example 3 is repeated, but by using an oil having number average molecular weight 13.000 (Fomblin~ ?60).
After 24 hours a weight loss of the fluid equal to 0.16%
is determined. The Example is summarized in Table 1.
(AF 2787/031/EST) zo EXAMPLE 7 (comparative) Example 6 is repeated without the invention additive.
After 24 hours a weight loss of the fluid equal to 52.2 is determined. The Example is summarized in Table 1.
EXAMPLE 8 (comparative) Example 6 is repeated, but by using' 0.05 g of the fol-lowing additive of formula (VI) described in USP 6,083,600:
( CH3CH2CH2 ) ~-N-CH~CF20 ( CF2CF20 ) ~ ( CF2C ) dCFzCH2-N- ( C:~i2CH2CH3 ) ~
ha-ving number average molecular weight 2000.
24 hours elapsed, a weight loss of the fluid equal to 0.25% is determined. The Example is summa:eized in Table y.
EXAMPLE 9 (comparative) Example ? is repeated but by using 1° of the stabilizing additive having the following formula (VIl-):
p2N ~ ~ OCHZCF2(OCFzCF2)m(OCFZ)nOCF2CHz0 S ~ N02 wherein the number average molecular weight of the (per)fluoropolyether chain is 1966 and m/n - 1.2, prepared according to the Example l of European patent application No.
03008436.
24 hours elapsed, a weight loss of the fluid equal to 0.420 is determined. The Example is summarized in Table 1.
(AF 2787/031/EST) A grease is prepared by mixing 70o by weight of Fomblin~
M30 having molecular weight 9,800, with 30o by weight of PTFE. The grease is additived with la by weight of the addi-tive prepared according to the Example ? and then subjected to the stability test to Lewis acids for greases. At the end of the test a per cent weight loss of 1.6°s is determined. The Example is summarized in Table 1.
EXAMPLE 11 (comparative) Example 10 is repeated, but in absence of the invention additive. At the end of the test, a per cent weight loss of 66o is detrmined. The Example is summarized in Table ~.
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(AF' 2787/03?/EST;
Claims (16)
1. Compounds formed of (per)fluoropolyether chains and end groups having a pyridine structure, having the following structural formula:
T1-CW1-O-R f-CW2-T2 (I) wherein T1, T2, equal to or different from each other, have the following meanings:
F. CF3, C2F5, (C2F4)C1;
- CH2-B-Y, CH (CF3) O-Y, wherein:
- B = O, S;
wherein R1, R2, R3, R9, equal to or different from each other, are H, F, C1-C8 linear or branched perfluoroalkyl, NO2, CN, preferably H
and/or C1-C8 linear or branched perfluoroalkyl;
with the proviso that at least one of the two end groups T1, T2 is CHI-B-Y or CH (CF3) O-Y as above defi-ned;
W1, W2. equal to or different from 'each other, are -F, -CF3;
- Rf is a (per)fiuoropolyoxyalkylene chain formed of one or more repeating units, statistically distribu-ted in the chain, having the following structure:
(CFXO), (CF2CF2O, (CF2CF2CF20), (CF2CF2CF2CF2O), (CR5R6CF2CF20), (CF (CF3) CF2O), (CF2CF (CF3) 0), wherein X = F, CF3; R5 and R6, equal to or different from each other, are selected from H, C1, perfluo-roalkyl from 1 to 4 carbon atoms;
the number average molecular weight of R f being from 400 to 10,000, preferably from 800 to 5,000.
T1-CW1-O-R f-CW2-T2 (I) wherein T1, T2, equal to or different from each other, have the following meanings:
F. CF3, C2F5, (C2F4)C1;
- CH2-B-Y, CH (CF3) O-Y, wherein:
- B = O, S;
wherein R1, R2, R3, R9, equal to or different from each other, are H, F, C1-C8 linear or branched perfluoroalkyl, NO2, CN, preferably H
and/or C1-C8 linear or branched perfluoroalkyl;
with the proviso that at least one of the two end groups T1, T2 is CHI-B-Y or CH (CF3) O-Y as above defi-ned;
W1, W2. equal to or different from 'each other, are -F, -CF3;
- Rf is a (per)fiuoropolyoxyalkylene chain formed of one or more repeating units, statistically distribu-ted in the chain, having the following structure:
(CFXO), (CF2CF2O, (CF2CF2CF20), (CF2CF2CF2CF2O), (CR5R6CF2CF20), (CF (CF3) CF2O), (CF2CF (CF3) 0), wherein X = F, CF3; R5 and R6, equal to or different from each other, are selected from H, C1, perfluo-roalkyl from 1 to 4 carbon atoms;
the number average molecular weight of R f being from 400 to 10,000, preferably from 800 to 5,000.
2. Compounds according to claim I, wherein the (per) fluoronolyether chain R f is selected from the fol-lowing Structures:
(A) -(CF2CF(CF3)O)a(CFXO)b- Or - (CF2CF (CF3) O) a (CFXO) b-CF2 (R' f) CF2-O- (CF2CF (CF3) O) a (CFXO) b-wherein R'f is a fluoroaikylene group from 1 to 4 C
atoms; X is F or CF3; a and b are integers such that the number average molecular weight is within the above range; a/b is between 10 and 100;
(B) - (CF2CF 2O) c (CF2O) d (CF2 (CF2) z O) h-wherein c, d and h are inetgers such that the number verage molecular weight is within she above range;
c/d is between 0.1 and 10; h/(c+d) is between 0 and .05, z is 2 or 3; h can also be equal to 0;
(C) - (CF2CF (CF3) O) a (CF2CF2O) f (CFXO) g-wherein X is F or CF3; e, f, g are integers such shat the number average molecular weight is within the above range; e/(f+g) is between 0.1 and 10; f/g is between 2 and 10;
(D) - (CF2 (CF2) Z O) S-wherein s is an integer such as to give the above molecular weight, z has the already defined meaning;
(E) - (CR5R6CF2CF2O) j'- or - (CR5R6CF2CF2O) p'-R ' f-O-- (CR5R6CF2CF2O) q'-wherein R5 and R6 are equal to or different from e-ach other and selected from H, C1 or perfluoroalkyl from 1 to 4 C atoms; R' f is a fluoroalkylene group from 1 to 4 C atoms; j', p' and q' are integers such as to have a molecular weight as that above indica-ted;
(F) - (CF(CF3)CF2O)j or - (CF (CF3) CF2O) j -R' f-O- (CF (CF3) CF2O) j"-wherein R' f is a fluoroalkylene group from 1 to 4 C
atoms; j" being an integer such as to give the above molecular weight.
(A) -(CF2CF(CF3)O)a(CFXO)b- Or - (CF2CF (CF3) O) a (CFXO) b-CF2 (R' f) CF2-O- (CF2CF (CF3) O) a (CFXO) b-wherein R'f is a fluoroaikylene group from 1 to 4 C
atoms; X is F or CF3; a and b are integers such that the number average molecular weight is within the above range; a/b is between 10 and 100;
(B) - (CF2CF 2O) c (CF2O) d (CF2 (CF2) z O) h-wherein c, d and h are inetgers such that the number verage molecular weight is within she above range;
c/d is between 0.1 and 10; h/(c+d) is between 0 and .05, z is 2 or 3; h can also be equal to 0;
(C) - (CF2CF (CF3) O) a (CF2CF2O) f (CFXO) g-wherein X is F or CF3; e, f, g are integers such shat the number average molecular weight is within the above range; e/(f+g) is between 0.1 and 10; f/g is between 2 and 10;
(D) - (CF2 (CF2) Z O) S-wherein s is an integer such as to give the above molecular weight, z has the already defined meaning;
(E) - (CR5R6CF2CF2O) j'- or - (CR5R6CF2CF2O) p'-R ' f-O-- (CR5R6CF2CF2O) q'-wherein R5 and R6 are equal to or different from e-ach other and selected from H, C1 or perfluoroalkyl from 1 to 4 C atoms; R' f is a fluoroalkylene group from 1 to 4 C atoms; j', p' and q' are integers such as to have a molecular weight as that above indica-ted;
(F) - (CF(CF3)CF2O)j or - (CF (CF3) CF2O) j -R' f-O- (CF (CF3) CF2O) j"-wherein R' f is a fluoroalkylene group from 1 to 4 C
atoms; j" being an integer such as to give the above molecular weight.
3. Compounds according to claim 2, wherein the perfluoro-polyether structures R f in the compounds of formula (I) are selected from the structures (A) and (B).
4. Compounds according to claims 1-3, wherein the (per)fluoropolyether chains are linked by an ether func-tion to the carbon atom in alpha position with respect to the nitrogen atom of the pyridine ring Y.
5. Lubricating compositions comprising:
- an oil or a grease having a perfluoropolyether structure;
- from 0.05% to 10% by weight, preferably from 0.1% to 5% by weight on the total of the composition, of compounds of claims 1-4.
- an oil or a grease having a perfluoropolyether structure;
- from 0.05% to 10% by weight, preferably from 0.1% to 5% by weight on the total of the composition, of compounds of claims 1-4.
6. Compositions according to claim 5, wherein the perfluoro-polyether oils have structures belonging to the following classes:
(1) E-O-(CF(CF3)CF2O)m'(CFXO)n'-E' wherein:
X is equal to F or CF3;
E and E', equal to or different from each other, are selected from CF3, C2F5 or C3F7;
m' and n' are integers such that the m'/n' ratio is between 20 and 1,000 and the product viscosity is between 10 and 4,000 cSt; the various units are sta-tistically distributed along the chain;
(2) C3F7O-(CF(CF3)CF2O)o'-D
wherein:
D is equal to -C2F5 or -C3F7;
o' is an integer such that the product viscosity is within the above range;
(3) {C3F7O-(CF(CF3)CF2O)p'-CF(CF3)-}2 wherein:
p' is an integer such that the compound viscosity is within the above range;
(4) E-O-(CF(CF3)CF2O)q'(C2F4O)r'(CFX)s'-E' wherein:
X is equal to F or CF3;
E and E', equal to or different from each other, are as above;
q', r' and s' are integers and can also have the 0 value, and such that the product viscosity is within the above range;
(5) E-O-(C2F4O)t'(CF2O)u'-E' wherein:
E and E', equal to or different from each other, are as above;
t' and u' are integers such that the t'/u' ratio is between 0.1 and 5 and the product viscosity is wi-thin the above range;
(6) E-O-(CF2CF2CF2O)v'-E' wherein:
E and E', equal to or different from each other, are as above;
v' is a number such that the product viscosity is within the above range;
(7) D-O- (CF2CF2O)z'-D' wherein:
D and D', equal to or different from each other, are selected between C2F5 or C3F7;
z' is an integer such that the product viscosity is within the above range;
the perfluoropolyether structures of the classes from (1) to (7) having a viscosity determined at 20°C from 30 to 100.000 cSt, preferably from 100 to 2,000 cSt.
(1) E-O-(CF(CF3)CF2O)m'(CFXO)n'-E' wherein:
X is equal to F or CF3;
E and E', equal to or different from each other, are selected from CF3, C2F5 or C3F7;
m' and n' are integers such that the m'/n' ratio is between 20 and 1,000 and the product viscosity is between 10 and 4,000 cSt; the various units are sta-tistically distributed along the chain;
(2) C3F7O-(CF(CF3)CF2O)o'-D
wherein:
D is equal to -C2F5 or -C3F7;
o' is an integer such that the product viscosity is within the above range;
(3) {C3F7O-(CF(CF3)CF2O)p'-CF(CF3)-}2 wherein:
p' is an integer such that the compound viscosity is within the above range;
(4) E-O-(CF(CF3)CF2O)q'(C2F4O)r'(CFX)s'-E' wherein:
X is equal to F or CF3;
E and E', equal to or different from each other, are as above;
q', r' and s' are integers and can also have the 0 value, and such that the product viscosity is within the above range;
(5) E-O-(C2F4O)t'(CF2O)u'-E' wherein:
E and E', equal to or different from each other, are as above;
t' and u' are integers such that the t'/u' ratio is between 0.1 and 5 and the product viscosity is wi-thin the above range;
(6) E-O-(CF2CF2CF2O)v'-E' wherein:
E and E', equal to or different from each other, are as above;
v' is a number such that the product viscosity is within the above range;
(7) D-O- (CF2CF2O)z'-D' wherein:
D and D', equal to or different from each other, are selected between C2F5 or C3F7;
z' is an integer such that the product viscosity is within the above range;
the perfluoropolyether structures of the classes from (1) to (7) having a viscosity determined at 20°C from 30 to 100.000 cSt, preferably from 100 to 2,000 cSt.
7. Compositions according to claim 6, wherein the perfluoro-polyether oils are those of the classes (1), (4), (5).
8. Compositions according to claims 5-7, comprising anti-rust, anti-oxidant or anti-wear additives.
9. Compositions according to claims 5-7, wherein the grease contains the perfluoropolyether oil and thickeners se-lected from PTFE, sodium terephthalamate, calcium or li-thium soaps, polyurea.
10. Compositions according to claim 9 containing additives selected from dispersing agents preferably surfactants, in particular non ionic, having a perfluoropolyether or perfluoroalkyl structure; talc or inorganic fillers, an-ti-rust, anti-oxidant or anti-wear additives.
11. A process to obtain the compounds of claims 1-4, compri-sing the following steps:
a) formation of an alcoholate or thiolate, by reaction of a compound-having a (per)fluoropolyoxyalkylene structure of formula:
T'1-CW1-O-R f-CW2-T'2 (II) wherein:
R f, W1 and W2 have the above meanings;
T'1 and T'2, equal to or different from each other, represent and end group selected from the following: CH2OH, CH2SH, CH(OH)CF3, F, CF3, C2F5, (C2F4)Cl;
with the proviso that at least one of the two end groups T'1 and/or T'2 is equal to CH2OH, CH2SH or CH(OH)CF3;
with an organic or inorganic base, in organic sol-vent inert under the reaction conditions;
b) reaction of the alcoholate or thiolate obtained in step a) with a pyridine compound of formula wherein R1, R2, R3, R4 have the above meaning, Q is halogen selected from Cl, Br, I, wherein the ratio of the equivalents between the al-coholate or thiolate function of the (per)fluo-rinated chain and the pyridine compound (III) is from 1 to 0.5, preferably from 0.8 to 0.6, in an or-ganic solvent inert under the reaction conditions, at a temperature in the range 20°C-100°C, preferably 40°C-80°C;
c) product isolation from the reaction mass by means of the known methods of the prior art.
a) formation of an alcoholate or thiolate, by reaction of a compound-having a (per)fluoropolyoxyalkylene structure of formula:
T'1-CW1-O-R f-CW2-T'2 (II) wherein:
R f, W1 and W2 have the above meanings;
T'1 and T'2, equal to or different from each other, represent and end group selected from the following: CH2OH, CH2SH, CH(OH)CF3, F, CF3, C2F5, (C2F4)Cl;
with the proviso that at least one of the two end groups T'1 and/or T'2 is equal to CH2OH, CH2SH or CH(OH)CF3;
with an organic or inorganic base, in organic sol-vent inert under the reaction conditions;
b) reaction of the alcoholate or thiolate obtained in step a) with a pyridine compound of formula wherein R1, R2, R3, R4 have the above meaning, Q is halogen selected from Cl, Br, I, wherein the ratio of the equivalents between the al-coholate or thiolate function of the (per)fluo-rinated chain and the pyridine compound (III) is from 1 to 0.5, preferably from 0.8 to 0.6, in an or-ganic solvent inert under the reaction conditions, at a temperature in the range 20°C-100°C, preferably 40°C-80°C;
c) product isolation from the reaction mass by means of the known methods of the prior art.
12. A process according to claim 11, wherein the steps a) +
b) can be simultaneously carried out, preferably in the presence of a phase transfer agent; or they can be carri-ed out in sequence.
b) can be simultaneously carried out, preferably in the presence of a phase transfer agent; or they can be carri-ed out in sequence.
13. A process according to claim 12, wherein the phase trans-fer agent is a phosphonium or a quaternary ammonium salt, preferably selected between tetrabutylammonium hydroxide or tetramethylammonium chloride.
14. A process according to claims 11-13, wherein, when steps a) and b) are simultaneously carried out, the ratio by weight between the solvent and the (per)fluorinated al-cohol or thiol is from 0.5 to 10, preferably from 2 to 5;
the ratio between the base equivalents and the (per)fluorinated alcohol or thiol equivalents ranges from 2 to 10; the equivalents of the phase transfer agent, when used, are in a ratio with the equivalents of the (per)fluorinated alcohol or thiol from 0.01 to 0.1.
the ratio between the base equivalents and the (per)fluorinated alcohol or thiol equivalents ranges from 2 to 10; the equivalents of the phase transfer agent, when used, are in a ratio with the equivalents of the (per)fluorinated alcohol or thiol from 0.01 to 0.1.
15. A process according to claims 11-13, wherein, when steps a) and b) are carried out in sequence, the ratio between the base equivalents and those of the compound of struc-ture (II) ranges from 1.1 to 2, preferably from 1.2 to 1.5.
16. Use of the compounds according to Claims 1-4 as stabili-zing additives of oils and greases having a perfluoro-polyether structure towards Lewis acids, even at high temperatures.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI2203A000992 | 2003-05-20 | ||
| IT000992A ITMI20030992A1 (en) | 2003-05-20 | 2003-05-20 | PERFLUOROPOLITEREI ADDITIVES. |
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| CA2467422A1 true CA2467422A1 (en) | 2004-11-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002467422A Abandoned CA2467422A1 (en) | 2003-05-20 | 2004-05-18 | Perfluoropolyether additives |
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| US (1) | US7399735B2 (en) |
| EP (1) | EP1479753B1 (en) |
| JP (1) | JP4589031B2 (en) |
| CA (1) | CA2467422A1 (en) |
| DE (1) | DE602004023996D1 (en) |
| IT (1) | ITMI20030992A1 (en) |
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| JP2003082088A (en) * | 2001-09-17 | 2003-03-19 | Sony Corp | Perfluoropolyether-based compound, lubricant comprising the same and recording medium using the lubricant |
| ITMI20020804A1 (en) * | 2002-04-17 | 2003-10-17 | Ausimont Spa | ADDITIVES FOR PERFLUOROPOLYEREAL OILS |
| AU2003268708A1 (en) * | 2002-10-01 | 2004-04-23 | Matsumura Oil Research Corp. | Perfluoropolyether compound and lubricant and magnetic disk using same |
-
2003
- 2003-05-20 IT IT000992A patent/ITMI20030992A1/en unknown
-
2004
- 2004-05-11 DE DE602004023996T patent/DE602004023996D1/en not_active Expired - Lifetime
- 2004-05-11 EP EP04011149A patent/EP1479753B1/en not_active Expired - Lifetime
- 2004-05-18 CA CA002467422A patent/CA2467422A1/en not_active Abandoned
- 2004-05-18 JP JP2004147911A patent/JP4589031B2/en not_active Expired - Fee Related
- 2004-05-20 US US10/849,168 patent/US7399735B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110760361A (en) * | 2019-09-24 | 2020-02-07 | 中国石油化工股份有限公司 | Perfluoropolyether lubricating grease and preparation method thereof |
| CN110760361B (en) * | 2019-09-24 | 2022-07-26 | 中国石油化工股份有限公司 | Perfluoropolyether lubricating grease and preparation method thereof |
| CN111876220A (en) * | 2020-08-04 | 2020-11-03 | 中国石油化工股份有限公司 | Chemical-medium-resistant fluorine-silicon lubricating grease and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1479753A3 (en) | 2006-09-06 |
| JP4589031B2 (en) | 2010-12-01 |
| EP1479753A2 (en) | 2004-11-24 |
| ITMI20030992A1 (en) | 2004-11-21 |
| US7399735B2 (en) | 2008-07-15 |
| EP1479753B1 (en) | 2009-11-11 |
| US20040235685A1 (en) | 2004-11-25 |
| DE602004023996D1 (en) | 2009-12-24 |
| JP2004346318A (en) | 2004-12-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |